Mechanism of octahedral substitution in nonaqueous media. Part VI. Rate of solvolysis of trans-dichloro- and trans-chloronitro-bis(ethylenediamine)cobalt(III) ions in formamide. Rate of replacement of chloride by thiocyanate in chloronitro-complex ion in sulpholan

Abstract

The rates of solvolysis of trans-dichloro- and trans-chloronitro-complex ions have been determined in formamide. The results agree with the previous observation that an increase in the polarity of the solvent leads to an increase in the rate of replacement of chloride in the dichloro- but not the chloronitro-complex ion.

The replacement of chloride by thiocyanate in chloronitro-complex ion in sulpholan (tetrahydrothiophen 1,1-dioxide) proceeded with complete retention of configuration. A limiting thiocyanate-independent rate was observed at relatively high thiocyanate concentration. The ion-association constant and the rate constant for the rearrangement of the ion aggregate were determined.